Preparation of azine dyestuff images



Patented Dec. 26, 1950 PREPARATION OF AZINE DYESTUFF IMAGES Willy A. Schmidt and Joseph A. Sprung, Easton,

Pa assignors to General Aniline & Film Corporation, New York, N. Y., a corporationof Delaware No Drawing. Application July 11, 1947, Serial No. 760,508

8 Claims.

The present invention relates to color photography and more particularly to color-formers capable of yielding azine dyestuff images when present during the development by means of primary aromatic amines of an exposed silver halide emulsion.

Our copending application Serial No. 577,134, filed February 9, 1945, now abandoned, discloses the preparation of azine dyestuff images by colorformin development of an exposed silver halide emulsion in the presence of a color-former which is an aromatic amine containing in meta-position to the amino group, the grouping -NHZ wherein Z is a substituent which is more electronegative than hydrogen, such as, phenyl, acyl, cyano, and the like. It is also stated in said application that similar results may be achieved when replacing the amino color-formers by phenolic color-formers and in this connection reference was made to the employment as a color-former of 3-hydroxy-benzenesulfon-p-toluidide.

Rather peculiarly, however, it has been ascertained that azine dye formation by ring closure of the intermediary-formed quinoneimine only takes place with the phenolic color-formers when the carbon atom in meta-position to the phenolic hydroxyl group is substituted by a sulfonamido grouping, to wit, the grouping -NI-I SOzR, wherein R has the value subsequently enumerated.

The particular reason for this phenomenon is not readily apparent. It would app ar, however, that the phenolic hydroxyl group on l-position is not as powerful as the amino group in directing ring closure and that it is only capable of so operating when the meta-position of the phen01 is substituted by the strongly electron-drawing sulfonamido group. Despite the theory which is involved, it is a fact that the only phenols which we have been able to effectively employ in the preparation of azine dye images by the color-forming development method are those in which the position meta to the hydroxyl group is substituted by the aforesaid sulfonamido group.

It is, accordingly, an object of the present invention to produce azine dyestuff images by the color development of a silver halide emulsion containing an aromatic phenol bearing in meta-position to the hydroxyl group a sulfonamido group.

It is a further object of the present invention to provide silver halide emulsions containing as color-formers aromatic phenols substituted in meta-position to the phenolic group by a sulfonamid group and which when reacted with the oxidation products of a primary aromatic amino developer yield azine dyestufi images.

vention will become apparent as the description proceeds.

The color-formers which are contemplated by the present invention are typified by the following formulae:

and

NHSOzR wherein R is aliphatic, such as, methyl, ethyl, propyl, butyl, amyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, and the like, or aromatic, such as, phenyl or naphthyl, acylphenyl, such as, acetylphenyl, propionylphenyl, and the like, alkylphenyl, such as, toluyl, ethylphenyl, and the like, acylaminophenyl, such as, acetylaminophenyl, laurylaminophenyl, stearylaminophenyl, and the like, and X is hydrogen, alkyl, such as, methyl, ethyl, propyl, butyl, and the like, aromatic as above, or sulfo.

Examples of compounds falling within the above category and which we have found to be suitable for the production of the desired azine dyestuff images are the following? NHS 020m 3-hydroxymethanesulfonanllide OH 3-hydroxy'propanesulfon-p-toluidlde ---NHS 0 2C EH11 3-hydroxypentanesulfonanilide 3-hydroxyo ctadecanesulfonanilide 3-hydroxydodecanesulfon-p-toluidide 3'-hydroxydodecanesulfonanilide 4-hydroxybutanesu1fon-2-naphthalide NHSO2C 15 37 2-hydroxy- (N-octadecanesulfonyl) sulfanilic acid -NHSOzC1s s1 4-hydroxyoctadecanesu1fon-2-nap11tha1ide --NH S O 2 (116 33 3 '-hydroxyhexade canesulfonanilide 3 -hydroxy- (4-acetamidobenzenesulfonanilide) 3'hydroxyhenzenesulfonanilide 4-hydrcxybenzenesulfon-Z-naphthalide NHS OzC -NH2 3!-hydroxy- (-aminobenzenesulfonanilide) -NHS 02- CH3 3-hydroxy-p-to1uenesu1fonani1ide (17) 7 (I311 NHS Oz-O-NHG o CmHra 3.-hydroxy- (4-dodccylamidobenzenesulfonanilide) NHSOz-ONHC'O 0111115 2 hyr11'0xy-N- (4mctadecylamidophenylsulfonyl '-sulfanilic acid 4-hy droxy- 4-acetamidobenz enesulfon-Zmaphthalide) These compounds can be prepared by methods usual in the art. For'instance, the' alkylsulfonyb amino-phenols are prepared by condensing the corresponding"alkylsulionyl'chloride with the desired 3'-amino -phenoli The preparation of substituted S-amino-l-naphthols such as is describediby Lees 18v Thorpe; ,J; Chem. $004191, Aneii'ective method for. preparing.

1303 (1907). the alkylsulfonyll chlorides involves the heating to a temperaturerof about 200 C". ofithednvolved alkyl halide With sodium-sulfitez to produce the troduced as the'last: step While employing for this purposev the corresponding" acyli chloride},

llhezreaction'hy Which'the azine dyestuffs are produced involves two co-nversionszwhich'may, take place spontaneously or in an observable sequence; The first reaction involves the-conventionalfort- 'mation of the quinoneimine dyeand the second the ring closure of the quinoneimine to the desired azine. Often in order to effect the second reaction, it is desirable to treat the quinoneimine with an alkali, such as, sodium hydroxide. The azine formed may be present as the anhydride but upon acidification the true azine salt is formed which possesses a characteristically brilliant color.

The invention may be realized in various ways. One method of effecting the formation of the azine dyestuff images comprises exposing a silver halide emulsion and subjecting it to the action of a primary aromatic amino developer containing one of the aforesaidcolor-forming components. Again, the silver halide emulsion may be exposed, developed to black and white and subsequently subjected to the action of such a color developer. On the other hand, the color-forming component may be incorporated in the emulsion and after exposure subjected to the action of a primar aromatic amino, developer.

It is, of course, evident that in the latter case it is necessary to employ the color-formin components in a form in which they are fast to diffusion in the photographic emulsion. Methods by which this result may be achieved are disclosed in U. S. P. 2,186,852, 2,186,851, 2,186,849, 2,186,734, 2,186,733, 2,186,732, 2,179,244, and the like. It is preferred, however, to make the color formers fast to diilusion by incorporating into the molecule of the phenol a radical having an alkyl chain of 5 carbon atoms or more, preferably 12 or more, such as, dodecyl, myristyl, stearyl,oleyl,

octadecyl, or the like. The long alkyl chain may a be present in the sulfonamido group as indicated above or may appear as a substituent in another position of the molecule.

To facilitate the incorporation of the colorformers in the emulsions or in the'developer, the compounds may contain substituents which increase their solubility in aqueous solutions. Such groups are, for instance, sulfonic acid groups, carboxylic acid groups, hydroxy polyethenoxy ether groups and the like. Examples of compounds containing water solubilizing groups other than the sulfonamido group have been mentioned above.

The following examples will serve to illustrate the invention but it is to be understood that the invention is not limited thereto.

Example I To 100 g. of a photographic silver halide emulsion is added 0.5 gram of 3-hydroxyoctadecanesulfonanilide. The emulsion is then coated on a transparent film base and dried. After exposure the film is developed in a color-forming developer comprisin Water cc 1,000 Sodium sulphite g 0.5 p-Diethylaminoaniline g 2.5 Sodium carbonate g 70 Potassium bromide g 2.5

A silver plus a purple quinoneimine dye image is formed. Upon treatment with sodium hydroxide a brown azine dye was obtained. Upon removal of the silver by bleaching in potassium ferricyanide solution and subsequent fixing, a bluish-magenta azine dye resulted.

Example II An exposed photographic silver bromide emulsion was developed in a color-forming developer of the following composition:

turns to. brownish-black. After. removal of the silver image, a' blue-magenta dye image remains. Upon immersioninto dilute. hydrochloric acid, a reddish-orange dye image appears.

Example III The procedure is the same as in Example I excepting that there is employed B-hydroxydodecanesulfonanilide. The final azine dye image obtained is bluish-magenta. Y

Example IV The procedure is the same as in Example I excepting that there is employed 2-hydroxy-N- (octadecylsulfonyl)-sulfanilic acid. By processing as in Example I a red-magenta azine dye is obtained.

Example V The procedure is the same as in Example I except that there is employed 3'-hydroxy-(4- stearamidobenzenesulfonanilide). A bluish-magenta azine dye image is obtained.

Example VI The procedure is the same as in Example I except that there is employed 3-hydroxyl-myristamidobenzenesulfonanilide). The final azine dye image obtained is bluish-magenta.

Example VII The procedure is the same a in Example II except that there is employed 3-hydroxy-(4- acetamidobenzenesulfonanilide). The final azine dye image obtained is reddish-orange.

Example VIII The procedure is the same as in Example II except that there is employed 3-hydroxy-(4- aminobenzenesulfonanilide)'. The final azine dye image obtained is reddish-orange.

Example IX The procedure is the same as in Example I except that 3'-hydroxy-4'wulfo-( i-myristamidobenzenesulfonanilide) is employed. The final azine dye image obtained is bluish-magenta.

Various modifications of the invention will occur to persons skilled in the art and we, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.

We claim:

1. The process of producing azine dyestuff images in a photographic silver halide emulsion which comprises exposing the emulsion and developing the same with a primary aromatic amino developer in the presence of an aromatic phenol capable of coupling in the 4-position and containing a sulfonamido group, the nitrogen atom of which is directly linked to the carbon atom in meta-position to the phenolic hydroxyl group.

2. A photographic silver halide emulsion containing an aromatic phenol capable of reacting in the 4-position with the oxidation products of a rllrimary :aromatic amino developer to pro duce an azine dye, said phenolwhaving asulionamido group, the nitrogen atom of which is directly linked to the carbon atom in meta position'to the phenolic 'hydroxyl group and said phenol containing a radical rendering it fast to diflusion in the photographic emulsion.

3. A photographic developer containin a primary aromatic amino developing compound and an aromatic molar-forming component capable of reacting in :the 4-.position withxthe oxidation products not said developing compound zto'ayield an azine: dye :and comprising :an aaromaticrphenol containing a :sulfonamido group, iathe :nitrogen atom of which is 5 directlylinked to the carbon atom in meta-position to the phenolic hydroxyl group.

4. The "process as defined in L claim 1 wherein the aromatic phenol is selected from the class consisting of compounds *of the following 'formulae:

and

wherein R is selected i from the class consisting of aliphatic and aromatic radicals and 'X is-a member of the class consisting of hydrogen, a1- kyl, aromatic and sulfa-radicals.

5. A photographic silver :halide emulsion as defined inelaim ,2 wherein the aromatic phenol isselectejd .from the class consisting. of compoundsrof the followingformulae:

and

:wherein .R is selected ff-rom;.the eclass ic nsis in of aliphaticqand aromatic radicals :and K115 :a memberwf the :.class consisting of hydr0gen.; a1- ckyl, aromaticuand sulfo radicals.

:,6. Aphotographic developer asdefineddngclalm :3 "wherein the aromatic phenol is selected :from the; class consisting of compoundspf 'thejollow- ;ing;formu1ae:

and

WILEY A. SCHMIDT.

JOSEPH *SPRUNG.

REFERENCES CI'EED The following vreferences are of record in the file of 'thispatent:

UNITED STATES PATENTS Number *Name *Date 2,312,004 Schneider etal. Feb. 23,1943 23623598 Vittumetal Nov. 14,' ;1944 2369,929 *Vittum et-ail. V "'Feb.-20, 2945' 2;423';'-730 Sal-niinen et a1. July 8, -1947 Kendall *et al. 'May'"l=1,-1948 

1. THE PROCESS OF PRODUCING AZINE DYESTUFF IMAGES IN A PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH COMPRISES EXPOSING THE EMULSION AND DEVELOPING THE SAME WITH A PRIMARY AROMATIC AMINO DEVELOPER IN THE PRESENCE OF AROMATIC PHENOL CAPABLE OF COUPLING IN THE 4-POSITION AND CONTAINING A SULFONAMIDO GROUP, THE NITROGEN ATOM OF WHICH IS DIRECTLY LINKED TO THE CARBON ATOM IN META-POSITION TO THE PHENOLIC HYDROXYL GROUP. 